Isotope analysis method (δ¹³C) in clarified apple juice

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Komatiites constrain molybdenum isotope composition of the Earth's mantle

In order to estimate the Mo isotope composition and Mo abundance in the Bulk Silicate Earth (BSE), a total of thirty komatiite samples from five localities on three continents were analyzed using an isotope dilution double spike technique. Calculated Mo concentrations of the emplaced komatiite lavas range from 25±325±3 to 66±22 ng/g66±22 ng/g, and the inferred Mo concentrations in the deep mantle sources of the komatiites range between 17±417±4 and 30±12 ng/g30±12 ng/g, with an average value of 23±7 ng/g23±7 ng/g (2SE). This average value represents our best estimate for the Mo concentration in the BSE; it is identical, within the uncertainty, to published previous estimates of 39±16 ng/g39±16 ng/g, but is at least a factor of 2 more precise. The Mo isotope compositions of the komatiite mantle sources overlap within uncertainty and range from View the MathML sourceδMo98=−0.04±0.28 to 0.11±0.10‰0.11±0.10‰, with an average of 0.04±0.06‰0.04±0.06‰ (2SE). This value is analytically indistinguishable from published Mo isotope compositions of ordinary and enstatite chondrites and represents the best estimate for the Mo isotope composition of the BSE. The inferred δ98Mo for the BSE is therefore lighter than the suggested average of the upper continental crust (0.3 to 0.4‰). Thus, from the mass balance standpoint, a reservoir with lighter Mo isotope composition should exist in the Earth's mantle; this reservoir can potentially be found in subducted oceanic crust. The similarity of δ98Mo between chondritic meteorites and estimates for the BSE from this study indicates that during the last major equilibration between Earth's core and mantle, i.e., the one that occurred during the giant impact that produced the Moon, chemical and isotopic equilibrium of Mo between Fe metal of the core and the silicate mantle was largely achieved.

Zircons, isotope ratios and element analyses from tonalite and oxide gabbro of the mid-ocean ridge from ODP Hole 176-735B

A limiting factor in the accuracy and precision of U/Pb zircon dates is accurate correction for initial disequilibrium in the 238U and 235U decay chains. The longest-lived-and therefore most abundant-intermediate daughter product in the 235U isotopic decay chain is 231Pa (T1/2 = 32.71 ka), and the partitioning behavior of Pa in zircon is not well constrained. Here we report high-precision thermal ionization mass spectrometry (TIMS) U-Pb zircon data from two samples from Ocean Drilling Program (ODP) Hole 735B, which show evidence for incorporation of excess 231Pa during zircon crystallization. The most precise analyses from the two samples have consistent Th-corrected 206Pb/238U dates with weighted means of 11.9325 ± 0.0039 Ma (n = 9) and 11.920 ± 0.011 Ma (n = 4), but distinctly older 207Pb/235U dates that vary from 12.330 ± 0.048 Ma to 12.140 ± 0.044 Ma and 12.03 ± 0.24 to 12.40 ± 0.27 Ma, respectively. If the excess 207Pb is due to variable initial excess 231Pa, calculated initial (231Pa)/(235U) activity ratios for the two samples range from 5.6 ± 1.0 to 9.6 ± 1.1 and 3.5 ± 5.2 to 11.4 ± 5.8. The data from the more precisely dated sample yields estimated DPazircon/DUzircon from 2.2-3.8 and 5.6-9.6, assuming (231Pa)/(235U) of the melt equal to the global average of recently erupted mid-ocean ridge basaltic glasses or secular equilibrium, respectively. High precision ID-TIMS analyses from nine additional samples from Hole 735B and nearby Hole 1105A suggest similar partitioning. The lower range of DPazircon/DUzircon is consistent with ion microprobe measurements of 231Pa in zircons from Holocene and Pleistocene rhyolitic eruptions (Schmitt (2007; doi:10.2138/am.2007.2449) and Schmitt (2011; doi:10.1146/annurev-earth-040610-133330)). The data suggest that 231Pa is preferentially incorporated during zircon crystallization over a range of magmatic compositions, and excess initial 231Pa may be more common in zircons than acknowledged. The degree of initial disequilibrium in the 235U decay chain suggested by the data from this study, and other recent high precision datasets, leads to resolvable discordance in high precision dates of Cenozoic to Mesozoic zircons. Minor discordance in zircons of this age may therefore reflect initial excess 231Pa and does not require either inheritance or Pb loss.

Isotope ratios of osmiun, carbon and oxygen of Miocene sediments and benthic foraminifera

Seawater 187Os/188Os ratios for the Middle Miocene were reconstructed by measuring the 187Os/188Os ratios of metalliferous carbonates from the Pacific (DSDP 598) and Atlantic (DSDP 521) oceans. Atlantic and Pacific 187Os/188Os measurements are nearly indistinguishable and are consistent with previously published Os isotope records from Pacific cores. The Atlantic data reported here provide the first direct evidence that the long-term sedimentary 187Os/188Os record reflects whole-ocean changes in the Os isotopic composition of seawater. The Pacific and the Atlantic Os measurements confirm a long-term 0.01/Myr increase in marine 187Os/188Os ratios that began no later than 16 Ma. The beginning of the Os isotopic increase coincided with a decrease in the rate of increase of marine 87Sr/86Sr ratios at 16 Ma. A large increase of 1? in benthic foraminiferal delta18O values, interpreted to reflect global cooling and ice sheet growth, began approximately 1 million years later at 14.8 Ma, and the long-term shift toward lower bulk carbonate delta13C values began more than 2 Myr later around 13.6 Ma. The post-16 Ma increase in marine 187Os/188Os ratios was most likely forced by weathering of radiogenic materials, either old sediments or sialic crust with a sedimentary protolith. We consider two possible Miocene-specific geologic events that can account for both this increase in marine 187Os/188Os ratios and also nearly constant 87Sr/86Sr ratios: (1) the first glacial erosion of sediment-covered cratons in the Northern Hemisphere; (2) the exhumation of the Australian passive margin-New Guinea arc system. The latter event offers a mechanism, via enhanced availability of soluble Ca and Mg silicates in the arc terrane, for the maintenance of assumed low CO2 levels after 15 Ma. The temporal resolution (three samples/Myr) of the 187Os/188Os record from Site 598, for which a stable isotope stratigraphy was also constructed, is significantly higher than that of previously published records. These high resolution data suggest oscillations with amplitudes of 0.01 to 0.02 and periods of around 1 Myr. Although variations in the 187Os/188Os record of this magnitude can be easily resolved analytically, this higher frequency signal must be verified at other sites before it can be safely interpreted as global in extent. However, the short-term 187Os/188Os variations may correlate inversely with short-term benthic foraminiferal delta18O and bulk carbonate delta13C variations that reflect glacioeustatic events.

Isotope geochemistry of Ninetyeast Ridge basalts

The Ninetyeast Ridge lavas have Sr and Nd isotopic ratios intermediate between those of Indian Ocean MORBs and those of the very enriched Kerguelen hot spot. In an Nd-Sr isotope diagram, they also plot close to the fields of St. Paul Island lavas and of the early magmatism on Kerguelen Archipelago. The Ninetyeast Ridge lavas were generated by mixing among at least three components: a depleted, MORB-type component, such as the one erupted today on the Southeast Indian Ridge; a very enriched, high- Sr/ Sr, low-epsilon-Nd, OIB-type component (the Kerguelen hot spot); and an OIB-type component comparable to that sampled from the St. Paul (and Amsterdam) lavas. The Ninetyeast Ridge lavas show a typical Dupal anomaly signature and Pb, Sr, and Nd isotopic systematics indicate that the Kerguelen hot spot was involved in the ridge's formation as the Indian plate moved northward. The different sites cored during ODP Leg 121 show a trend in their isotopic compositions, from less radiogenic Pb/ Pb ratios and intermediate 87Sr/86Sr and 143Nd/**Nd ratios in the oldest lavas (Site 758) toward more radiogenic 206Pb/204Pb, higher epsilon-Nd, and lower 87Sr/86Sr values in the youngest lavas (Site 756). The lavas from Site 757 have 206Pb/204Pb ratios intermediate between those of the lavas from Sites 756 and 758 and higher 87Sr/86Sr and lower epsilon-Nd values. The relative proportions of the hot spot(s) and MORB component have evolved with time, reflecting differences of tectonic setting: the relative proportion of the Kerguelen hot spot component appears lower in the younger Site 756 lavas than in the older lavas from Sites 757 and 758. Site 756 coincides with the beginning of rifting at the Southeast Indian Ridge, about 43 Ma ago. The formation of the early Kerguelen Archipelago lavas may have drained most of the plume-derived material toward the Antarctic plate. Alternatively, the proximity of the spreading-ridge axis may account for the isotopic similarity of the Site 756 lavas to young lavas erupted on the Southeast Indian Ridge, from 33? to 37?S. The older lavas of Ninetyeast Ridge may have formed when the hot spot and ridge axis did not exactly coincide. The involvement of the third component, a St. Paul hot spot, in the genesis of the Ninetyeast Ridge lavas, especially for the Site 756 lavas, is clearly indicated by Sr, Pb, and Nd isotope systematics and also by trace element ratios. These data, together with those from the Kerguelen Plateau, indicate that the Kerguelen hot spot has been active more or less continuously in the South Indian Ocean for at least 115 Ma. This could indicate that the plume, and by inference the Dupal anomaly, is deep seated in origin.

Element concentrations, and Sr and Os isotope ratios of DSDP Leg 92 metalliferous carbonates

The Os concentration and isotopic composition of metalliferous carbonates deposited on the East Pacific Rise over the past 28 Ma are reported with complimentary Sr isotope data. Variations in the Os isotopic composition of these samples are interpreted as a record of past changes in the Os isotopic composition of seawater. These results are consistent with isotopic analyses of leachable Os in pelagic clays which have also been interpreted as a record of the 187Os/186Os ratio of seawater through time (Pegram et al., 1992, doi:10.1016/0012-821X(92)90132-F). The metalliferous carbonate record clearly shows that seawater Os and Sr isotope systems are partially decoupled from one another over the past 28 Ma. Accelerated weathering of ancient organic-rich sediments is suggested as a possible mechanism to account for this decoupling and the rapid increase in the 187Os//186Os ratio of seawater over the past 15 Ma. This rapid increase suggests that the seawater Os record can potentially be used as a stratigraphic tool in some Neogene marine deposits.

Strontium and neodymium concentrations and isotope compositions in fossil fish teeth and pore waters at ODP Sites 130-807 and 125-786

We analyzed Nd and Sr isotopic compositions of Neogene fossil fish teeth from two sites in the Pacific in order to determine the effect of cleaning protocols and burial diagenesis on the preservation of seawater isotopic values. Sr is incorporated into the teeth at the time of growth; thus Sr isotopes are potentially valuable for chemostratigraphy. Nd isotopes are potential conservative tracers of paleocirculation; however, Nd is incorporated post-mortem, and may record diagenetic pore waters rather than seawater. We evaluated samples from two sites (Site 807A, Ontong Java Plateau and Site 786A, Izu-Bonin Arc) that were exposed to similar bottom waters, but have distinct lithologies and pore water chemistries. The Sr isotopic values of the fish teeth appear to accurately reflect contemporaneous seawater at both sites. The excellent correlation between the Nd isotopic values of teeth from the two sites suggests that the Nd is incorporated while the teeth are in chemical equilibrium with seawater, and that the signal is preserved over geologic timescales and subsequent burial. These data also corroborate paleoseawater Nd isotopic compositions derived from Pacific ferromanganese crusts that were recovered from similar water depths (Ling et al., 1997; doi:10.1016/S0012-821X(96)00224-5). This corroboration strongly suggests that both materials preserve seawater Nd isotope values. Variations in Pacific deepwater e-Nd values are consistent with predictions for the shoaling of the Isthmus of Panama and the subsequent initiation of nonradiogenic North Atlantic Deep Water that entered the Pacific via the Antarctic Circumpolar Current.

Element contents and isotope composition of sediments and basalts from DSDP Site 78-543

Twenty-four piston core sediment samples and 13 sediments and 3 basalts from DSDP Leg 78 Site 543 were analyzed for Sr, Nd and Pb isotopic compositions. The results show sediment with highly radiogenic Pb (206Pb/204Pb up to 19.8) and rather radiogenic Sr and unradiogenic Nd has been deposited in the region since the Cretaceous. The source of this sediment is probably the Archean Guiana Highland, which is drained by the Orinoco River. Pb and Sr isotopic compositions and sediment thickness decrease and 143Nd/144Nd increases northward due to a decrease in turbiditic component. This decrease is partly due to the damming action of basement ridges. Rare earth concentrations in the sediments are somewhat low, due to the abundance of detrital and biogenic components in the sediment and rapid sedimentation rates. Both positive and negative Ce anomalies occur in the surface sediments, but only positive Ce anomalies occur in the Site 543 sediments. It is unlikely that sediment subducted to the source region of Lesser Antilles arc magmas could be the cause of negative Ce anomalies in those magmas. Isotopic compositions of Site 543 basalts show some effect of contamination by seawater-basalt reaction products and sediments. Beyond this, however, they are typical of "normal" depleted MORB.

Alkali contents, Sr isotope and U-Th-Pb data for ocean crust vein minerals from DSDP Holes 27-261, 61-462A, and 72-516F

Cation exchange experiments (ammonium acetate and cation resin) on celadonite-smectite vein minerals from three DSDP holes demonstrate selective removal of common Sr relative to Rb and radiogenic Sr. This technique increases the Rb/Sr ratio by factors of 2.3 to 22 without significantly altering the age of the minerals, allowing easier and more precise dating of such vein minerals. The ages determined by this technique (Site 261 - 121.4+/-1.6 m.y.; Site 462A - 105.1+/-2.8 m.y.; Site 516F - 69.9+/-2.4 m.y.) are 34, 54 and 18 m.y. younger, respectively, than the age of crust formation at the site; in the case of site 462A, the young age is clearly related to off-ridge emplacement of a massive sill/flow complex. At the other sites, either the hydrothermal circulation systems persisted longer than for normal crust (10-15 m.y.), or were reactivated by off-ridge igneous activity. Celadonites show U and Pb contents and Pb isotopic compositions little changed from their basalt precursors, while Th contents are significantly lower. Celadonites thus have unusually high alkali/U,Th ratios and low Th/U ratios. If this celadonite alteration signature is significantly imprinted on oceanic crust as a whole, it will lead to very distinctive Pb isotope signatures for any hot spot magmas which contain a component of aged subducted recycled oceanic crust. Initial Sr isotope ratios of ocean crust vein minerals (smectite, celadonite, zeolite, calcite) are intermediate between primary basalt values and contemporary sea water values and indicate formation under seawaterdominated systems with effective water/rock ratios of 20-200.

Trace element abundances and Sr and Nd isotope compositions in bulk sediments from DSDP Legs 6 and 20

Rare earth element and Nd isotopic data for ten representative samples of Lower Cretaceous to Miocene pelagic sediments from the western Pacific indicate a wide range of compositions for sediments being subducted beneath the Mariana and Volcano arcs. All samples are enriched in light rare earth elements and show negative Eu and Ce anomalies. The values of e-Nd range from +0.6 to -7.3. These data are used to calculate the Bulk Western Pacific Sediment (BWPS), which is characterized by low Sr/Nd (10), Ba/La (13), and e-Nd (-5.2) and high 87Sr/86Sr (0.7078) compared to that of Mariana and Volcano arc lavas. This composite sediment is used to refine a mixing model for the origin of Mariana and Volcano arc melts. Some lavas from the northern Mariana Arc have Ba/La higher than that of BWPS, which indicates that a third component is required. The high Ba/La in the mantle source for these lavas is interpreted to result from multiple episodes of fluid fractionation. The mixing model indicates that a minor amount of sediment and a low proportion of metasomatic fluid fluxes the mantle source at a late stage when the subarc mantle is already highly metasomatized. This model also suggests that the mantle source for arc melts is affected more by metasomatic fluids than by melting or bulk mixing of sediments.

Isotope ratios of sediments from DSDP Hole 47-397 (Table 1)

We report the Sr, Nd and Pb isotopic compositions (1) of 66 lava flows and dikes spanning the circa 15 Myr subaerial volcanic history of Gran Canaria and (2) of five Miocene through Cretaceous sediment samples from DSDP site 397, located 100 km south of Gran Canaria. The isotope ratios of the Gran Canaria samples vary for 87Sr/86Sr: 0.70302-0.70346, for 143Nd/144Nd: 0.51275-0.51298, and for 206Pb/204Pb: 18.76-20.01. The Miocene and the Pliocene-Recent volcanics form distinct trends on isotope correlation diagrams. The most SiO2-undersaturated volcanics from each group have the least radiogenic Sr and most radiogenic Pb, whereas evolved volcanics from each group have the most radiogenic Sr and least radiogenic Pb. In the Pliocene-Recent group, the most undersaturated basalts also have the most radiogenic Nd, and the evolved volcanics have the least radiogenic Nd. The most SiO2-saturated basalts have intermediate compositions within each age group. Although the two age groups have overlapping Sr and Nd isotope ratios, the Pliocene-Recent volcanics have less radiogenic Pb than the Miocene volcanics. At least four components are required to explain the isotope systematics of Gran Canaria by mixing. There is no evidence for crustal contamination in any of the volcanics. The most undersaturated Miocene volcanics fall within the field for the two youngest and westernmost Canary Islands in all isotope correlation diagrams and thus appear to have the most plume-like (high 238U/204Pb) HIMU-like composition. During the Pliocene-Recent epochs, the plume was located to the west of Gran Canaria. The isotopic composition of the most undersaturated Pliocene-Recent volcanics may reflect entrainment of asthenospheric material (with a depleted mantle (DM)-like composition), as plume material was transported through the upper asthenosphere to the base of the lithosphere beneath Gran Canaria. The shift in isotopic composition with increasing SiO2-saturation in the basalts and degree of differentiation for all volcanics is interpreted to reflect assimilation of enriched mantle (EM1 and EM2) in the lithosphere beneath Gran Canaria. This enriched mantle may have been derived from the continental lithospheric mantle beneath the West African Craton by thermal erosion or delamination during rifting of Pangaea. This study suggests that the enriched mantle components (EM1 and EM2) may be stored in the shallow mantle, whereas the HIMU component may have a deeper origin.